Azo compounds

ABSTRACT

The present invention relates to novel dyestuffs of formula (I) 
                         
wherein the substituents have the meanings defined in the claims, the production of such dyestuffs, the use of these dyestuffs and material dyed or printed by such dyestuffs.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation application of U.S. application Ser.No. 10/473,783, filed Oct. 2, 2003, issued as U.S. Pat. No. 7,101,983,the contents of which are incorporated herein by reference.

The present invention relates to novel disperse dyes, to theirpreparation, and to the use thereof for dyeing and printing regeneratedor synthetic hydrophobic materials and/or blends comprising regeneratedor synthetic hydrophobic materials.

The present invention relates to novel dyestuffs of formula (I)

wherein

-   X signifies H; halogen, preferably Cl or Br; —CN or —NO₂,-   R¹ signifies C₁₋₆-alkyl; substituted C₂₋₄-alkyl, preferably    substituted by one or more substituents of the group consisting of    halogen, —CN, —OC₁₋₂-alkyl, —OCOC₁₋₃-alkyl, —OC₆H₅ and —C₆H₅;    C₃₋₄-alkenyl; substituted C₃₋₄-alkenyl, preferably substituted by    —Cl or —Br; C₃₋₄-alkinyl, preferably propargyl;    C₂₋₄-alkylene-OCO—C₁₋₃-alkyl; C₂₋₄-alkylene-O(CO)O—C₁₋₃-alkyl;-    C₁₋₃alkylene-COO—R⁵;-    —C₁₋₃-alkylene-COO—C₂₋₃-alkylene-N-phthalimid;    C₁₋₃-alkylene-COOCH₂COOR⁵ or C₁₋₃-alkylene-COOCH₂COR⁶,    -   wherein R⁵ signifies C₁₋₄-alkyl; C₁₋₂-alkoxyethyl; C₃₋₄-alkenyl;        C₃₋₄-alkinyl; cinnamyl; phenoxyethyl; phenyl-C₁₋₃alkyl;        tetrahydrofurfuryl-2; phenyl or phenyl, which is substituted by        —CH₃, —OCH₃, —COOCH₃ or —COOC₂H₅,        -   R⁶ signifies C₁₋₄-alkyl; phenyl or substituted phenyl,            preferably substituted by one or more substituents of the            group consisting of —CH₃, —OCH₃, —OC₂H₅, halogen and —OH,-   R² signifies H; C₁₋₆-alkyl; substituted C₂₋₄-alkyl, preferably    substituted by one or more substituents of the group consisting of    halogen, —CN, —OH, —OC₁₋₂-alkyl, —OCOC₁₋₃-alkyl, —OC₆H₅ and —C₆H₅;    C₃₋₄-alkenyl; substituted C₃₋₄-alkenyl, preferably substituted by    —Cl or —Br; C₃₋₄-alkinyl, preferably propargyl;    C₂₋₄-alkylene-OCO—C₁₋₃alkyl; C₂₋₄-alkylene-O(CO)O—C₁₋₃-alkyl;    C₁₋₃alkylene-COO—R⁵; C₁₋₃-alkylene-COOCH₂COOR⁵ or    C₁₋₃-alkylene-COOCH₂COR⁶,    -   wherein R⁵ and R⁶ have the same meaning as defined above,        with the provisos that if X is —NO₂, H or halogen, then R² is        not a C₁₋₆ alkyl radical,-   R³ signifies H; —NHCO-A¹; —NHCOO-A² or —NHCONH-A³,    -   wherein        -   A¹ signifies H; C₁₋₄-alkyl; C₂₋₃-alkenyl; phenyl or            substituted C₁₋₂-alkyl, preferably substituted by one or            more substituents of the group consisting of —OH, —Cl, —OCH₃            and —C₆H₅,        -   A² signifies C₁₋₄-alkyl or substituted C₂₋₄-alkyl,            preferably substituted by one or more substituents of the            group consisting of —Cl, —OCH₃ and —OC₂H₅,        -   A³ signifies H or C₁₋₄-alkyl, and-   R⁴ signifies H; halogen or C₁₋₄alkoxy,    with the provisos that if R⁴ signifies C₁₋₄alkoxy, then R¹ is not    C₁₋₃alkylene-COO—R⁵;    with the provisos that if R³ and R⁴ both signify H, then R¹ is not    C₁₋₃alkylene-COO—R⁵;    as well as mixtures thereof.

Any alkyl present is linear or branched unless indicated to thecontrary.

Any substituted alkyl present can be optionally substituted by one ormore identical or different substituent.

Halogen atoms are preferably chlorine or bromine.

In formula I, preferably

-   X signifies H; —CN or —NO₂,-   R¹ signifies C₁₋₄-alkyl; substituted C₂₋₄-alkyl, preferably    substituted by one or more substituents of the group consisting of    halogens, —CN, —OC₁₋₂-alkyl, —OCO—C₁₋₃-alkyl and —OC₆H₅;    C₃₋₄-alkenyl; benzyl; propargyl; —C₂₋₄-alkylene-OCO—C₁₋₃-alkyl;    —C₂₋₄-alkyleneO(CO)O—C₁₋₃-alkyl; C₁₋₂-alkylene-COO—R⁵;    —C₁₋₃-alkylene-COO—C₂₋₃-alkylene-N-phthalimid;    C₂₋₃-alkylene-COOCH₂COOR⁵ or C₂₋₃-alkylene-COOCH₂COR⁶,    -   wherein    -   R⁵ signifies C₁₋₄-alkyl; C₁₋₂-alkoxyethyl; C₃₋₄-alkenyl;        C₃₋₄-alkinyl; cinnamyl; phenoxyethyl; phenyl-C₁₋₃alkyl;        tetrahydrofurfuryl-2; phenyl or phenyl, which is substituted by        —CH₃, —OCH₃, —COOCH₃ or —COOC₂H₅,        -   R⁶ signifies C₁₋₄-alkyl; phenyl or substituted phenyl,            preferably substituted by one or more substituents of the            group consisting of —CH₃, —OCH₃, —OC₂H₅, halogen and —OH,-   R² signifies H, C₁₋₄-alkyl; substituted C₂₋₄-alkyl, preferably    substituted by one or more substituents of the group consisting of    halogens, —CN, —OC₁₋₂-alkyl, —OCO—C₁₋₃-alkyl and —OC₆H₅;    C₃₋₄-alkenyl; benzyl; propargyl; —C₂₋₄-alkylene-OCO—C₁₋₃-alkyl;    —C₂₋₄-alkyleneO(CO)O—C₁₋₃-alkyl; C₁₋₂-alkylene-COO—R⁵;    C₂₋₃-alkylene-COOCH₂COOR⁵ or C₂₋₃-alkylene-COOCH₂COR⁶,    -   wherein        -   R⁵ signifies C₁₋₄-alkyl; C₁₋₂-alkoxyethyl; C₃₋₄-alkenyl;            C₃₋₄-alkinyl; cinnamyl; phenoxyethyl; phenyl-C₁₋₃alkyl;            tetrahydrofurfuryl-2; phenyl or phenyl, which is substituted            by —CH₃, —OCH₃, —COOCH₃ or —COOC₂H₅,        -   R⁶ signifies C₁₋₄-alkyl; phenyl or substituted phenyl,            preferably substituted by one or more substituents of the            group consisting of —CH₃, —OCH₃, —OC₂H₅, halogen and —OH,            with the proviso that if X is H or —NO₂, then R² is not a            C₁₋₄-alkyl,-   R³ signifies H; NHCO—C₁₋₂-alkyl; NHCO—C₁₋₂-alkyl substituted by —OH,    —Cl or —OCH₃; and-   R⁴ signifies H or C₁₋₂-alkoxy,    with the provisos that if R⁴ signifies C₁₋₂-alkoxy, then R¹ is not    C₁₋₂alkylene-COO—R⁵;    with the provisos that if R³ and R⁴ both signify H, then R¹ is not    C₁₋₃alkylene-COO—R⁵;    as well as mixtures thereof.

Particularly preferred are dyestuffs of formula (I) and mixturesthereof, wherein

-   X signifies H; —CN or —NO₂,-   R¹ signifies C₁₋₄-alkyl; substituted C₂₋₄-alkyl, preferably    substituted by one or more substituent of the group consisting of    —Cl, —CN, —OC₁₋₂-alkyl, —OCOC₁₋₃-alkyl and —OC₆H₅; allyl; benzyl;    propargyl; —C₂H₄—OCO—C₁₋₃-alkyl; —C₂H₄O(CO)O—C₁₋₃-alkyl;    C₁₋₂alkylene-COO—R⁵ or C₁₋₃-alkylene-COO—C₂H₄—N-phthalimid,-   R² signifies H; C₁₋₄-alkyl; allyl; propargyl; —C₂H₄OCO—C₁₋₃-alkyl;    C₁₋₂alkylene-COO—R⁵;-    —C₂H₄COOCH₂COOR⁵ or —C₂H₄COOCH₂COR⁶,    -   wherein        -   R⁵ signifies C₁₋₄-alkyl; C₁₋₂-alkoxyethyl; allyl; benzyl;            propargyl; cinnamyl; phenoxyethyl or tetrahydrofurfuryl-2,        -   R⁶ signifies C₁₋₂-alkyl or phenyl,            with the proviso that if X is H or —NO₂, then R² is not a            C₁₋₄-alkyl,-   R³ signifies —NHCO—C₁₋₂-alkyl and-   R⁴ signifies H or —OCH₃.    with the provisos that if R⁴ signifies —OCH₃, then R¹ is not    C₁₋₂alkylene-COO—R⁵;    with the provisos that if R³ and R⁴ both signify H, then R¹ is not    C₁₋₃alkylene-COO—R⁵;    as well as mixtures thereof.

Most preferred are dyestuffs of formula (I) and mixtures thereof,wherein

-   X signifies H,-   R¹ signifies —CH₃; —C₂H₅; allyl; benzyl; propargyl; —C₂H₄CN;    C₂H₄OCO—C₁₋₂-alkyl; —C₁₋₃-alkylene-COO—C₂H₄—N-phthalimid or    —C₂H₄—COO—R⁵,-   R² signifies H, —CH₃, —CH₂CH₃, —C₂H₄OCO—C₁₋₂-alkyl or —C₂H₄—COO—R⁵,    -   wherein        -   R⁵ signifies C₁₋₄-alkyl; C₁₋₂-alkoxyethyl; allyl; benzyl;            propargyl; phenoxyethyl or tetrahydrofurfuryl-2,-   R³ signifies —NHCOCH₃ and-   R⁴ signifies H.    with the provisos that if R³ and R⁴ both signify H, then R¹ is not    C₁₋₃alkylene-COO—R⁵;    as well as mixtures thereof.

The above-mentioned novel compounds as well as mixtures thereof are veryuseful disperse dyestuffs.

Production of these dyestuffs is effected by coupling a diazotized amineof formula (II)

with an amine of formula (III)

wherein all substituents have the same meanings as defined above.

Diazotization and coupling are effected by generally known processes.

The diazotization is carried out, for example using sodium nitrite inacid aqueous medium. The diazotization can also be carried out usingother diazotization agents, for example nitrosulfuric acid. Anadditional acid may be present in the reaction medium duringdiazotization, for example phosphoric acid, sulfuric acid, acetic acid,propionic acid, hydrochloric acid or mixtures of these acids, e.g.mixtures of phosphoric acid, and acetic acid. Diazotization isconveniently carried out within the temperature range of from −10 to 10°C., preferably from 0° C. to 5° C.

Coupling of the diazotized compound of formula (II) to the couplingcomponent of formula (III) is carried out in known manner, for examplein acid, aqueous or aqueous-organic medium, preferably within thetemperature range from 0° C. to 50° C., more preferably from 20° C. to40° C. Acid used are, for example hydrochloric acid, acetic acid,sulfuric acid or phosphoric acid. For example diazotization and couplingcan be carried out in the same reaction medium.

Alkali metal nitrites, such as, for example, sodium nitrite, in solidform or as an aqueous solution, or in nitrosylsulfuric acid are employedas the nitrosating agents.

The preparation of the diazonium ion, typically through the reactionwith excess nitrous acid or the like such as nitrosyl sulfuric acid atlow temperature to form the electrophilic ion Aryl-N₂ ⁺ is disclosed inthe literature e.g. Advanced Organic Chemistry, Fieser & Fieser, pages736-740 or Organische Chemie, K. Peter C. Vollhardt, pages 1154-1157, I.Auflage 1988.

The compounds of formulae (II) and (III) are known or may easily beproduced in a manner familiar to the person skilled in the art.

The new dyestuffs of formula (I) as well as mixtures thereof can be usedfor dyeing and printing semisynthetic and, preferably, synthetichydrophobic fiber materials, especially textile materials. Textilematerials consisting of blended fabrics containing such semisynthetichydrophobic fiber materials can also be dyed or printed by means of thedyes of this invention.

Suitable semisynthetic textile materials are mainly cellulose-2½acetate, cellulose triacetate polyamides and high molecular weightpolyesters as well as mixtures thereof with cellulose.

Synthetic hydrophobic textile materials consist mainly of lineararomatic polyester, for example of those consisting of terephthalic acidand glycols, in particular ethylene glycol or condensate of terephthalicacid and 1,4-bis(hydroxymethyl)cyclohexane; of polycarbonates, e.g.those consisting of α,α-dimethyl-4,4′-dihydroxydiphenylmethane andphosgene, and of fibers based on polyvinyl chloride and polyamide.

The hydrophobic synthetic materials can be in the form of sheet-like orthread-like structures, and can be processed, for example, to yarns orwoven, knitted or looped textile fabrics. The novel dyes are alsosuitable for dyeing hydrophobic synthetic material in the form of microfibers.

It is expedient to convert the novel dyes according to formula (I)before use into a dye formulation. This is done by milling the dye to anaverage particle size of 0.1 to 10 micron. Milling can be carried out inthe presence of dispersants. Typically, the wet dye is milled with adispersant, and thereafter dried under vacuum or by spray drying.Printing pastes and dyebaths can be prepared by adding water to theformulation so obtained.

The new dyestuffs according to formula (I) are applied to the textilematerials by known dyeing or printing methods, e.g. those described inFrench patent application No. 1.445.371. Typically, polyester fibermaterials are dyed from an aqueous dispersion by the exhaust process inthe presence of customary anionic or non-ionic dispersants and in thepresence or absence of customary swelling agents (carrier) in thetemperature range from 65° C. to 140° C. Cellulose-2½-acetate ispreferably dyed at a temperature from 65° C. to 85° C. and cellulosetriacetate at temperatures up to 115° C. The novel dyes are suitable fordyeing by the thermosol process, for the exhaust process, the continuousprocess and for printing as for modern imaging processes, e.g.thermo-transfer printing, ink-jet printing, hot melt inkjet printing orby conventional printing processes.

The thermosol process, the exhaust process and the continuous processare well known dyeing processes and are described for example in M.Peter and H. K. Rouette: “Grundlagen der Textilveredelung; Handbuch derTechnologie, Verfahren und Maschinen”, 13^(th) revised Edition, 1989,Deutscher Fachverlag GmbH, Frankfurt am Main, Germany, ISBN3-87150-277-4; wherein the following pages are of special interest:pages 460-461, 482-495, 556-566 and 574-587.

In the inkjet printing process, individual droplets of the ink aresprayed from a nozzle onto a substrate in a controlled manner. Thecontinuous inkjet method and the drop-on-demand method are employedpredominantly for this purpose. In the case of the continuous inkjetmethod, the droplets are produced continuously and droplets not neededfor printing are diverted into a collecting vessel and recycled. In thecase of the discontinuous drop-on-demand method, by contrast, dropletsare generated and printed as desired, i.e. droplets are only generatedwhen this is necessary for printing. The droplets may be generated forexample by means of a piezo inkjet head or by means of thermal energy(bubble jet).

In hot melt inkjet printer solid hot melt inks are loaded in a printercapable of melting the ink in the inkjet printer head, ejecting theliquid ink which quickly resolidifies upon impacting a substrate.Conventional hot melt inkjet printers operate with a printing head andinkjet temperature of about 120 to about 150° C. At those temperatures,the solid ink is melted to a low viscosity liquid, generally about 8 to25 cP when measured at jetting temperature.

Conventional printing processes are well known and differ in the way theprinting ink or printing paste is transfered to the substrate: Forexample, inks or pastes can be applied by raised type (e.g. letterpress, flexographic), from a planar surface (lithographic), from arecessed surface (intaglio) or through a stencil (silk screen).Different methods of application and different substrates requiredifferent properties in the ink.

The dyeings are carried out from an aqueous liquor by the exhaustprocess, and the liquor ration can be chosen from a wide range, forexample from 1:4 to 1:100, preferably from 1:6 to 1:50. The dyeing timeis from 20 to 90 minutes, preferably from 30 to 60 minutes. The dyeliquors can additionally comprise other additives, for example dyeingauxiliaries, dispersants, wetting agents and antifoams.

The liquor may also comprise mineral acids, such as sulfuric acid orphosphoric acid, or conveniently also organic acids, for example formicacid or acetic acid and/or salts, such as ammonium acetate, ammoniumsulfate or sodium sulfate. The acids mainly serve to adjust the pH ofthe dye liquors which is preferably in the range from 4 to 5.

The disperse dyes are usually present in the dye liquors in the form ofa fine dispersion. Suitable dispersants for the preparation of thisdispersion are e.g. anionic dispersants, such as aromatic sulfonicacid/formaldehyde condensates, sulfonated creosol oil/formaldehydecondensates, lignin sulfonates or copolymers of acrylic acid derivates,preferably aromatic sulfonic acid/formaldehyde condensates or ligninsulfonated, or nonionic dispersants based on polyalkylene oxidesobtainable, for examples, by polyaddition reaction from ethylene oxideor propylene oxide. Further suitable dispersants are listed in U.S. Pat.No. 4,895,981 or in U.S. Pat. No. 5,910,624. Suitable inks or pastescomprise a) at least one dye of the formula (I) or mixtures of compoundsof the formula (I), b) water or a medium including a mixture of waterand an organic solvent, an anhydrous organic solvent or a solid having alow melting point, and c) optionally further additives.

The inks or pastes preferably include a total amount of dyes of theabove formula (I). which is in the range from 1 to 35% by weight,especially in the range from 2 to 35% by weight, preferably in the rangefrom 2 to 30% by weight, more preferably in the range from 2.5 to 20% byweight, based on the total weight of the ink or paste. The inks include99-65% by weight, especially 98-65% by weight, preferably 98-70% byweight, more preferably 97.5-80% by weight, of an abovementioned mediumb), which includes water or a mixture of water and an organic solvent,an anhydrous organic solvent or a solid having a low melting point.

When said medium b) is a mixture including water and an organic solventor an anhydrous organic solvent, then the dye of formulae (I) ormixtures thereof are preferably completely dissolved in this medium.Preferably the dye of formulae (I) or mixtures thereof have a solubilityof not less than 2.5% by weight in this medium b) 0 at 20° C. When theink composition of the invention is used for printing papery substratesor hydrophobic substrates made of acetate-, polyester-, polyamide-,polyacrylnitrile-, polyvinylchloride- or polyurethane-polymers andblends thereof, the inks are preferably used together with the followingcompositions. When the medium is a mixture of water and an organicsolvent, the weight ratio of water to organic solvent is preferably inthe range from 99:1 to 1:99, more preferably in the range from 99:1 to50:50, particularly preferably in the range from 95:5 to 80:20. It ispreferable for the organic solvent which is included in the mixture withwater to be a water-soluble solvent or a mixture of variouswater-soluble solvents. Preferred water-soluble organic solvents areC₁₋₆-alcohols, preferably methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol andcyclohexanol; linear amides, preferably dimethylformamide ordimethylacetamide; ketones and keto alcohols, preferably acetone, methylethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone;water-miscible ethers, preferably tetrahydrofuran and dioxane; diols,preferably diols possessing 2 to 12 carbon atoms, e.g. 1,5-pentanediol,ethylene glycol, propylene glycol, butylene glycol, pentylene glycol,hexylene glycol, thiodiglycol and oligo- and poly-alkylene glycols,preferably diethylene glycol, triethylene glycol, polyethylene glycoland polypropylene glycol; triols, preferably glycerol and1,2,6-hexanetriol; mono-C₁₋₄-alkyl ethers of diols, preferablymono-C₁₋₄-alkyl ethers of diols possessing 2 to 12 carbon atoms,particularly preferably 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol,2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol,2-[2-(2-ethoxyethoxy)ethoxy]ethanol and ethylene glycol monoallyl ether;cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone,N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; cyclicesters, preferably caprolactone; sulphoxides, preferably dimethylsulphoxide and sulpholane. In a preferred composition, the medium as perb) includes water and at least 2 or more, more preferably 2 to 8,water-soluble organic solvents. Particularly preferred water-solublesolvents are cyclic amides, particularly 2-pyrrolidone,N-methylpyrrolidone and N-ethylpyrrolidone; diols, preferably1,5-pentanediol, ethylene glycol, thiodiglycol, diethylene glycol andtriethylene glycol; and mono-C₁₋₄-alkyl and di-C₁₋₄-alkyl ethers ofdiols, more preferably mono-C₁₋₄-alkyl ethers of diols possessing 2 to12 carbon atoms, particularly preferably2-[2-(2-methoxyethoxy)ethoxy]ethanol.

A preferred medium as per b) includes:

-   -   (i) 75 to 95 parts by weight of water and    -   (ii) 25 to 5 parts of one or more of the following solvents:        diethylene glycol, 2-pyrrolidone, thiodiglycol,        N-methylpyrrolidone, cyclohexanol, caprolactone, caprolactam and        1,5-pentanediol,        wherein the parts are by weight and all parts of (i) and (ii)        add up to 100.

Examples of further useful ink compositions including water and one ormore organic solvents are found in the Patent Specifications U.S. Pat.Nos. 4,963,189, 4,703,113, 4,626,284 and EP 425150A.

When the medium as per b) includes an anhydrous (i.e. less than 1% byweight of water) organic solvent, this solvent will have a boiling pointof 30 to 200° C., more preferably of 40-150° C., particularly preferablyof 50-125° C. The organic solvent can be water-insoluble, water-solubleor mixtures of such solvents. Preferred water-soluble organic solventsare all above-described water-soluble organic solvents and mixturesthereof. Preferred water-insoluble solvents include inter alia aliphatichydrocarbons; esters, preferably ethyl acetate; chlorinatedhydrocarbons, preferably CH₂Cl₂; and ethers, preferably diethyl ether;and mixtures thereof. When the liquid medium as per b) includes awater-insoluble organic solvent, it is preferable to add a polar solventto increase the solubility of the dye in the liquid medium. Examples ofsuch polar solvents are C₁₋₄-alcohols, preferably ethanol or propanol;ketones, preferably methyl ethyl ketone. The anhydrous organic solventcan consist of a single solvent or a mixture of 2 or more differentsolvents. When it is a mixture of different solvents, a mixtureincluding 2 to 5 different anhydrous solvents is preferred. This makesit possible to provide a medium as per b) which permits good control ofthe drying properties and of the stability of the ink composition instorage. Ink compositions including an anhydrous organic solvent ormixtures thereof are of particular interest when rapid drying times arerequired and especially when they are used for prints on hydrophobic andnon-absorbing substrates, such as plastic, metal and glass.

Preferred low-melting media have a melting point of 60 to 140° C. Usefullow-melting solids include long-chain fatty acids or alcohols,preferably those having a C₁₈₋₂₄-carbon chain, and sulphonamides.Conventional low-melting ink vehicles generally include variousproportions of waxes, resins, plasticizers, tackifiers, viscositymodifiers and antioxidants.

The ink composition and the printing pastes of the invention may furtherinclude as auxiliaries additional components which are normally used ininkjet inks or printing pastes, for example buffers, viscosityimprovers, surface tension improvers, fixation accelerants, biozides,corrosion inhibitors, levelling agents, drying agents, humefactants, inkpenetration additives, light stabilisers, UV absorbers, opticalbrighteners, coagulation reducers, ionic or nonionic surfactants andconducting salts. These auxiliaries are preferably added in an amount of0-5% by weight to inks. To printing pastes up to 70% by weight,especially up to 60% by weight, preferably up to 55% by weight, based onthe total weight of the printing paste.

To prevent precipitations in the ink compositions of the invention, thedyes used have to be purified clean. This can be done with commonlyknown purifying methods.

When the compositions of the invention are used for printing textilefibre materials, preference is given to using the followingcompositions.

When printing textile fibre materials, useful additives, besides thesolvents including water, are synthetic thickener, natural thickener ormodified natural thikeners which may include water-soluble nonioniccellulose ethers, alginates or bean gum ether. All, the water-solublenonionic cellulose ethers, the alginates and the bean gum ether, areused as thickeners to adjust the ink to a certain viscosity. Usefulwater-soluble nonionic cellulose ethers include for example methyl-,ethyl-, hydroxyethyl-, methylhydroxyethyl-, hydroxypropyl- orhydroxypropylmethyl-cellulose. Preference is given to methylcellulose orin particular hydroxyethylcellulose. Cellulose ethers are customarilyused in the ink in an amount of 0.01 to 2% by weight, especially 0.01 to1% by weight, preferably 0.01 to 0.5% by weight, based on the totalweight of the ink. Useful alginates include in particular alkali metalalginates, preferably sodium alginate. These are customarily used in theink in an amount of 0.01 to 2% by weight, especially 0.01 to 1% byweight, preferably 0.01 to 0.5% by weight, based on the total weight ofthe ink. Printing pastes include up to 70% by weight thickening agents,preferably up to 55% by weight thickening agents. In printing pastes thethickening agents are used in an amount of 3 to 70% by weight,especially 5 to 60% by weight, preferably 7 to 55% by weight, based onthe total weight of the printing paste. In the ink jet printing processpreference is given to ink compositions having a viscosity of 1 to 40mPa·s, especially 5 to 40 mPa·s, preferably 10 to 40 mPa·s. Inkcompositions having a viscosity of 10 to 35 mPa·s are particularlypreferred. Preference is given to ink compositions having a surfacetension of 15-73 mN/m, especially 20-65 mN/m, particularly preferably30-50 mN/m. Preference is given to ink compositions having aconductivity of 0.1-100 mS/cm, especially 0.5-70 mS/cm, particularlypreferably 1.0-60 mS/cm. The inks may further include buffer substances,for example acetate, phospate, borax, borate or citrate. Examples aresodium acetate, di-sodium hydrogen phosphate, sodium borate, sodiumtetraborate and sodium citrate.

The dyeings or printings thus obtained, have good all-round fastness;particularly noticeable are the thermo-migration fastness,thermo-fixation-, and pleating fastness, as well as the excellent wetfastness.

In the following examples, the parts and percentages are by weight. Thetemperatures are given in degrees Celsius.

EXAMPLE 1

Diazotization:

15.4 parts of 2-amino-5-nitrophenol are dissolved in 13.7 parts of cold30% sodium hydroxide solution. 36.5 parts of 30% HCl are added andafterwards during a period of 1 hour 6.9 parts of sodium nitrite as anaqueous solution (40%) are added at a temperature of 0-5° C. Thesolution is stirred for 2 hours at 0-5° C. and 0.1 part of aminosulfonicacid are added to destroy the excess of sodium nitrite.

Coupling:

A hot solution (95° C.) of 55.6 parts of3-(N-methyl-N-phenyl)amino-propionic acid-2′-N-phthalimido)-ethylesterin 156 parts glacial acetic acid is added continuously to the diazoniumsalt solution. The suspension is stirred at 35° C. and the pH isadjusted to 1.0 by addition of 3.5 parts of sodium acetate and 50 partsof acetic acid. The suspension is stirred for 20 h and the precipitateddyestuff is filtered off, washed with water and dried in the vacuum at60° C.

The isolated dyestuff of formula (IV)

has a λ_(max) of 514 nm (in DMF) and dyes polyester in red shades withgood fastness.

EXAMPLE 2

Diazotization:

The diazotization is done analogously as in Example 1.

Coupling: A solution of 32.9 parts of1-N,N-di-(2′-acetoxyethyl)-amino-3-acetylaminobenzene in 100 partsglacial acetic acid is added continuously to the diazonium saltsolution, followed by an addition of 300 parts water. Afterwards thetemperature of the solution is increased to 30° C. and the pH value isadjusted to 2 by addition of sodium acetate. The solution is stirred for24 hours at 30° C. The precipitated dyestuff is filtered off, washedwith water and dried in the vacuum at 60° C.

The isolated dyestuff of formula (V)

has a λ_(max) of 519 nm (in DMF) and dyes polyester in red shades withgood fastnesses.

EXAMPLE 3

Diazotization:

The diazotization is done analogously as in Example 1.

Coupling: A solution of 33.6 parts of a mixture of1-[N,N-di-(2′-acetoxyethyl)-amino]-3-acetylaminobenzene and1-[(N-acetoxyethyl-N-propionyloxyethyl)-amino]-3-acetylamino-benzene in100 parts glacial acetic acid is added continuously to the diazoniumsalt solution, followed by an addition of 300 parts water. Afterwardsthe temperature of the solution is increased to 30° C. and the pH valueis adjusted to 2 by addition of sodium acetate. The solution is stirredfor 24 hours at 30° C. The precipitated dyestuff is filtered off, washedwith water and dried in the vacuum at 60° C.

The isolated dyestuff is mixture of the compounds of formula (VIa) and(VIb)

with a λ_(max) of 519 nm (in DMF), which dyes polyester in red shadeswith good fastnesses.

Table 1 below, gives further dyestuffs of formula (Ia), which areproduced analogously to the procedures given in the preceding example.

All dyestuffs dye polyester fiber material in red shades with very goodfastness.

TABLE 1/EXAMPLES 4–25

(Ia) Ex. λ_(maz) DMF No. R⁴ R³ R² R¹ [nm] 4 H H —CH₂CH₃—CH₂CH₂—COO—CH₂—CH₂—N-phthalimid 518 5 H —CH₃ —CH₂CH₃—CH₂CH₂—COO—CH₂—CH₂—N-phthalimid 529 6 H —CH₃ —CH₃—CH₂CH₂—COO—CH₂—CH₂—N-phthalimid 527 7 H H —CH₃—CH₂—CH₂—COO—C₆H₄-4-COOCH₃ 508 8 H H —CH₂CH₃ —CH₂—CH₂—COO—C₆H₄-4-COOCH₃517 9 H H —CH₂CH₃ —CH₂—CH₂—COO—C₆H₄-4-OCH₃ 518 10 H H —CH₂CH₃—CH₂—CH₂—COO—C₆H₄-3-CH₃ 519 11 H H —CH₂CH₃ —CH₂CH₂CN 509 12 H —NHCOCH₃—CH₂CH₂OCOCH₃ —CH₂CH₂CN 513 13 H —NHCOCH₂CH₃ —CH₂CH₂OCOCH₃ —CH₂CH₂OCOCH₃519 14 H —NHCOCH₃ —CH₂CH₂OCOCH₃ —CH₂CH₂OCOC₂H₅ 519 15 H —NHCOCH₃—CH₂CH₂COOCH₃ —CH₂CH₂COOCH₃ 516 16 H —NHCOCH₃ —CH₂CH₂COOC₂H₅—CH₂CH₂COOC₂H₅ 518 17 H —NHCOCH₃ —CH₂CH═CH₂ —CH₂CH₂COOCH₂CH═CH₂ 522 18 H—NHCOCH₃ —CH₂C₆H₅ —CH₂CH₂COOCH₂COOCH₂C₆H₅ 520 19 H —NHCOCH₃—CH₂CH₂OCOCH₃ —CH₂—CH(OCOCH₃)CH₂CI 522 20 H —NHCOCH═CH₂ —CH₂CH₂OCOCH₃—CH₂CH₂OCOCH₃ 517 21 H —NHCOOCH₃ —CH₂CH₂COOCH₃ —CH₂CH₂COOC₂H₅ 515 22 H—NHCOCH₃ —CH₂COOCH₃ —CH₂CH₂COOCH₂COOCH₃ 503 23 Cl —NHCOC₆H₅ H—CH₂—CH₂COOCH₃ 505 24 H —NHCOC₂H₅ —CH₂—CH₂—COOCH₃ —CH₂—CH₂—COOCH₃ 516 25H —NHCOC₂H₅ —CH₂—CH₂—COOC₂H₅ —CH₂—CH₂—COOC₂H₅ 518 26 H —NHCOCH₃—CH₂—CH₂—COOCH₃ —CH₂—CH₂—COOC₂H₅ 517 27 H —NHCOCH₃ —CH₂—CH₃—CH₂—CH₂—COOCH₃ 528 28 H —NHCOCH₃ —CH₂—CH₃ —CH₂—CH₂—COOC₂H₅ 529 29 H—NHCOCH₃ —CH₂═CH₂ —CH₂—CH₂—COOCH₃ 521 30 H —NHCOH —CH₂—CH₂—COOC₂H₅—CH₂—CH₂—COOC₂H₅ 513 31 H —NHCOH —CH₂—CH₂—COOCH₃ —CH₂—CH₂—COOCH₃ 516 32H —NHCOH —CH₂—CH₂—OCOC₂H5 —CH₂—CH₂—OCOC₂H₅ 517 32 H —NHCOCH₃—CH₂—CH₂—OCH₃ —CH₂—CH₂—OCOC₂H₅ 523 33 H —NHCOCH₃ —CH₂—CH₂—OCH₃—CH₂—CH₂—COOCH₃ 521 34 H —NHCOCH₃ —CH₂—CH₂—OCH₃ —CH₂—CH₂—OCH₃ 529 35 H—NHCOCH₃ —CH₂—CH₂—OCH₃ —CH₂CH₂COOCH₂COOCH₂C₆H₅ 522 36 H —NHCOCH₃—CH₂—CH₂—OCOCH₃ —CH₂—CH₂—COOCH₃ 518 37 H —NHCOCH₃ —CH₂—CH(OH)—CH₃—CH₂—CH₂—COOCH₃ 520 38 H —NHCOCH₃ —CH₂—CH(OH)—CH₃ —CH₂—CH₂—COOC₂H₅ 52239 H —NHCOCH₃ —CH₂—CH OH —C₂H₅ —CH₂—CH₂—COOCH₃ 523 40 H —NHCOCH₃—CH₂—CH(OH)—CH₂—OC₆H₅ —CH₂—CH₂—COOCH₃ 522 41 H —NHCOCH₂OCH₃—CH₂—CH₂—COOC₂H₅ —CH₂—CH₂—COOC₂H₅ 516 42 H —NHCOCH₂OC₂H₅ —CH₂—CH₂—OCOCH₃—CH₂—CH₂—OCOCH₃ 518 43 H —NHCOCH₂Cl —CH₂—CH₂—COOCH₃ —CH₂—CH₂—COOCH₃ 51744 H —NHCOCH₃ H —CH₂CH₂—COO—CH₂—CH₂—N-phthalimid 525 45 H —NHCOCH₃ H—CH₂CH₂COOCH₂COOCH₂C₆H₅ 523 46 H —NHCOCH₃ H —CH₂CH₂COOCH₂COOC₂H₅ 524 47Cl —NHCOCH₃ H —CH₂—CH(OH)—CH₃ 514 48 Cl —NHCOCH₃ H —CH₂—CH(OH)—CH₂—Cl512

EXAMPLE 49

7.5 parts of potassium acetate and 5.0 parts of cupric acetate are addedto a solution of 11.8 parts of3-acetylamino-4-(2′-bromo-4′-nitro-6′-cyanophenylazo)-N,N-diethylanilinein 50 parts N-methylpyrrolidon at room temperature. The temperature ofthe solution is increased to 100° C. and the solution is stirred for 3hours at 100° C. 200 parts of water is added to get a suspension of thecopper complex intermediate. After filtration the wet residue is addedto 200 parts of 2N hydrochloric acid. The suspension is stirred tohydrolyse the intermediate to the final 2-hydroxy derivative within 3hours at 60° C.

The dyestuff is filtered off, washed with water and dried in the vacuumat 60° C.

The isolated dyestuff of formula (VII)

has a λ_(max) of 582 nm (in DMF) and dyes polyester in brillant violetshades with good fastnesses.

EXAMPLE 50

7.5 parts of potassium acetate and 5.0 parts of cupric acetate are addedto a solution of 11.83 parts of3-acetylamino-4-(2′-bromo4′,6′-dinitrophenylazo)-6-methoxy-1-N,N-diallyl-anilinein 50 parts dimethyl sulfoxide at room temperature. The temperature ofthe solution is increased to 75° C. and the solution is stirred for 3hours at 75° C. 200 parts of water is added to get a suspension of thecopper complex intermediate. After filtration the wet residue is addedto 200 parts of 2N hydrochloric acid. The suspension is stirred tohydrolyse the intermediate to the final 2-hydroxy derivative within 3hours at 60° C.

The precipitated dyestuff is filtered off, washed with water and driedin the vacuum at 60° C.

The isolated dyestuff of formula (VIII)

has a λ_(max) of 588 nm (in DMF) and dyes polyester in navy blue shadeswith good fastnesses.

Table 2 below, gives further dyestuffs of formula I, which are producedanalogously to the procedures given in the preceding example.

TABLE 2/EXAMPLES 51–63

(I) Ex. No. X R⁴ R³ R² R¹ λ^(max) DMF [nm] 51 —NO₂ —OCH₃ —NHCOCH₃—CH₂C(CH₃)═CH₂ —CH₂C(CH₃)═CH₂ 590 52 —NO₂ —OCH₃ —NHCOCH₃ —CH₂CH₂OCOCH₃—CH₂C≡CH 582 53 —NO₂ —OCH₃ —NHCOCH₃ —CH₂CH₂OCOCH₃ —CH₂CH₂OCOCH₃ 585 54—NO₂ —OCH₃ —NHCOCH₃ —CH₂CH₃ —CH₂CH═CHCl 589 55 —NO₂ —OC₂H₅ —NHCOCH₃—CH₂CH₂OCOCH₃ —CH₂CH₂OCOCH₃ 586 56 —NO₂ —OC₂H₅ —NHCOCH₃ —CH₂CH═CH₂—CH₂CH═CH₂ 590 57 —NO₂ —OCH₃ —NHCOCH₃ —CH₂CH₃ —CH₂CH₂COOCH₂COOCH₃ 592 58CN —OCH₃ —NHCOCH₃ —CH₂CH₃ —CH₂CH₂CN 595 59 CN —OCH₃ —NHCOCH₃ —CH₂CH═CH₂—CH₂CH═CH₂ 596 60 CN —OCH₃ —NHCOC₂H₅ —CH₂—C₆H₅ —CH₂—C₆H₅ 592 61 CN —OCH₃—NHCOCH₃ —CH₂CH₃ —CH₂—C₆H₅ 595 62 CN H —NHCOCH₂CH₃ —CH₂CH₃ —CH₂CH₃ 58363 Br H —NHCOCH₃ —CH₂CH₃ —CH₂CH₃ 565

APPLICATION EXAMPLE A

17.5 parts of the dyestuff according to example 1 in the form of themoist presscake are wet-ground by a known method with 32.5 parts of acommercial dispersing agent based on lignin sulfonates, and pulverizedto a powder. 1.2 parts of this dye preparation are added to 2000 partsof demineralized water of 70° C., which contains 40 parts of ammoniumsulfate; the pH value of the dye bath is set at 5 with 85% formic acid.100 parts of washed polyester fiber fabric are placed in this dye bath,the container is closed, heated to 130° C. over the course of 20minutes, and dyeing continues for a further 60 minutes at thistemperature. After cooling, the polyester fiber fabric is removed fromthe dye bath, rinsed, soaped and cleaned by reduction with sodiumhydrosulfite in the usual way. After thermo-fixation (180° C., 30 sec),a brilliant red dyeing is obtained with very good all-round fastness,especially fastness to light and sublimation, in particular excellentwet fastness. The dyestuffs of examples 2 to 63 may be used in analogousmanner, and dyeings with very good all-round fastness are obtained.

Dyeing polyester yarn can be carried out analogously with examples 2-63.

APPLICATION EXAMPLE B

2.5 parts of the dyestuff obtained in Example 1 are dissolved withstirring at 25° C. in a mixture of 20 parts diethyleneglycol and 77.5parts water to obtain a printing ink suitable for ink jet printing.

The dyestuffs of Examples 2 to 63 or dyestuff mixtures of Examples 1 to63 can also be used in a manner analogous to that described inApplication Example B.

APPLICATION EXAMPLE C

A printing paste according to the invention consists of

-   500 g of a thickener (bean gum ether e.g. Indalca™),-   10 g of a fixation accelerant (e.g. Printogen HDN™),-   10 g of a levelling agent (e.g. Sandogen CN™),-   10 g of a buffer and dispersant system for dyeing (eg. Sandacid PB™;    1:2) and-   10 g of a dye of example 1    and adding water up to 1000 g.

(Indalca was purchased from Cesalpinia S.p.A, Italy; Sandogen, Printogenand Sandacid are a trademarks of Clariant AG, Muttenz/Switzerland.)

This printing paste is used for printing papery substrates, textilefibre materials and plastic films and plastic transparencies.

The dyestuffs of Examples 2 to 63 or dyestuff mixtures of Examples 1 to63 can also be used in a manner analogous to that described inApplication Example C.

APPLICATION EXAMPLE D

A polyester Interlock fabric was printed with a conventional printingmachine using the printing paste of the APPLICATION EXAMPLE C. Theresulting printed fabric is dried for 3 minutes at 110° C. and thentreated with hot steam for 7 minutes at 175° C. The fabric was rinsedwith cold tap water for 5 minutes, and then rinsed for 5 minutes withdemineralised water. The so treated fabric was reductively cleansed in abath comprising 4 g/l Na₂CO₃, 2 g/l hydrosulfite sodium salt (85%) and 1g/l Lyogen DFT™ (Trademark of Clariant AG, Muttenz, Switzerland).Further rinsing for 15 minutes with tap water was followed by a finaldrying step. This leaves a polyester fabric with a brilliant red printwith very good all-round fastness, especially fastness to light andsublimation, in particular excellent wet fastness.

The dyestuffs of Examples 2 to 63 or dyestuff mixtures of Examples 1 to63 can also be used in a manner analogous to that described inApplication Example D.

APPLICATION EXAMPLE E

The ink jet printing composition is preferably prepared by heating themedium to 40° C. and then adding a dye of the example 1. The mixture isstirred until the dyes are dissolved. The composition is then cooleddown to room temperature and the further ingredients are added.

The fractions of the individual components of the ink compositions

-   6 parts of the dye of example 1,-   20 parts of glycerol and-   74 parts of water.

This ink composition is used for printing papery substrates, textilefibre materials and plastic films and plastic transparencies.

The dyestuffs of Examples 2 to 63 or dyestuff mixtures of Examples 1 to63 can also be used in a manner analogous to that described inApplication Example E.

APPLICATION EXAMPLE F

A polyester Interlock fabric was ink jet printed using the printing inkof the APPLICATION EXAMPLE E. The printed fabric was treated analouguslyto the post printing treatment of APPLICATION EXAMPLE D. This leaves apolyester fabric with a brilliant red print with very good all-roundfastness, especially fastness to light and sublimation, in particularexcellent wet fastness.

The dyestuffs of Examples 2 to 63 or dyestuff mixtures of Examples 1 to63 can also be used in a manner analogous to that described inApplication Example F.

1. A dyestuff according to formula (I)


2. A process for the production of a dyestuff according to claim 1,comprising the step of: coupling a diazotized amine of formula (II)

with an amine of formula (III)


3. A process for dyeing a textile material comprising the steps of:providing a textile material; providing a disperse dyestuff of formula(I) according to claim 1 or a mixture of disperse dyestuffs comprising adyestuff of formula (I) according to claim 1; and applying said dispersedyestuff of formula (I) or said mixture of disperse dyestuffs to saidtextile material.
 4. An inkjet printing process comprising the steps of:providing a substrate; providing an inkjet ink comprising a dispersedyestuff of formula (I) according to claim 1; applying said inkjet inkto said substrate.
 5. A composition comprising a dyestuff according toclaim
 1. 6. A composition according to claim 5 wherein the compositionis a printing paste or a printing ink or a inkjet printing ink or a hotmelt inkjet printing ink.
 7. Fibers or threads or materials producedthereof, which comprise fully or semi-synthetic, hydrophobic, organicmaterials dyed or printed with a dyestuff according to claim
 1. 8. A hotmelt inkjet printing process comprising the steps of: providing asubstrate; providing an hot melt inkjet ink comprising a dispersedyestuff of formula (I) according to claim 1; applying said hot meltinkjet ink to said substrate.